Soluble onium salts of halogenmethylated dibenzanthronyls



Patented Nov. 25, 1952 UNITED STATES SOLUBLE ONIUM SALTS OF HALOGEN- METHYLATED DIBENZA'NTHRONYLS David I. Randall, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application February 10, 1950, Serial No. 143,597

3 Claims.

This invention relates to the manufacture of new dyestuffs from the halogenmethyl derivatives of compounds of the dibenzanthronyl, dibenzanthrone, and isodibenzanthrone series.

In a co-pending application Serial No. 143,596, filed on February 10, 1950, there are described the halogenmethyl derivatives of members of the dibenzanthronyl, dibenzanthrone, and isodibenzanthrone series. It was pointed out in that application that the halogenmethyl derivatives to some degree have utility as dyes when used in a vatting process, and that these halogenmethyl derivatives have particular utility as intermediates for the preparation of soluble dyes. It is to the preparation of these soluble dyes that this application is directed.

Any halogenmethyl derivative of a clibenzanthronyl, dibenzanthrone, or isodibenzanthrone compound may be converted to a soluble dye by the process of this application, which comprises reacting the halogenmethylated compound with a thiourea compound or a tertiary amine. The reaction proceeds in accordance with one of the following equations:

(1) l lHr (2) Ar(OHzCl)11. 1LN(OHa)z Ar(OH2l T(OHa)aC1)'/L wherein Ar is the radical of a dibenzanthronyl, dibenzanthrone, or isodibenzanthrone compound and n is a number from 1 to 3. The thiourea of reaction 1 may be replaced by thiourea derivatives such as l-allylthiourea, l-methylthiourea, 1- phenylthiourea, 1,3-dimethylthiourea, 1,3-ethylenethiourea, 1,1,3-trimethylthiourea, and 1,1,3,3- tetramethylthiourea. The trimethyl amine of reaction 2 may be replaced by tertiary amines such as pyridine, picoline, isoquinoline, quinoline, diethylaminoethyl alcohol, triethylamine, and benzyldimethylamine.

The isothiouronium salts of the chlormethylated dibenzanthronyl, dibenzanthrone, and isodibenzanthrone compounds are prepared by heating a mechanically stirred mixture of the chlormethylated dibenzanthronyl, dibenzanthrone, or isodibenzanthrone compound and thiourea or a thiourea derivative under reflux for a period of about one-half hour. The reaction mixture is then diluted'with acetone or water, filtered and slurried or Washed with acetone. The product is dried by exposure to air. The resulting dyes are water-soluble and are substantive to paper, cotton, silk, nylon, and wool. They may be paste-printed on cotton, silk, and nylon, and developed by vat or acid aging methods Well known to the art. The isothiouronium salts of the dibenzanthronyl, dibenzanthrone, and isodibenzanthrone chlormethyl derivatives may be represented by the formula:

+ NR Rz Ar CHzSG A NRaRi 11 wherein Ar is the radical of a dibenzanthronyl, dibenzanthrone, or isodibenzanthrone compound, R1, R2, R3, and R4 are members of the group consisting of alkyl, alkylene, aryl, and hydrogen, of which R2 and R4 may together form a closed ring system; n is a number from 1 to 3; and A indicates a negative ion, such as chlorine, bromine, or sulfate.

The quaternary salts of the chlormethylated dibenzanthronyl, dibenzanthrone, and isodibenzanthrone compounds are prepared by heating a mixture of the chlormethylated dibenzanthronyl, dibenzanthrone, or isodibenzanthrone With a tertiary amine e. g. tri-rnethylamine pyridine. After heating for several hours the reaction mixture is diluted With acetone, filtered, and washed with acetone until the tertiary amine odor has been removed. The resulting dye is readily soluble in water. The resulting quaternary salts of the chlormethylated dibenzanthronyls, dibenzanthrones, and isodibenzanthrones may be represented by the following formulae:

wherein Ar has the same meaning as above; Q1,

Q2, and Q3 are members of the group consisting of alkyl, alkylol, and alkaryl; Z indicates the C atoms necessary to complete a 6-membered ring system; A and n have the same meanings as above. Print dyeings may be made from these quaternary salts of the chlormethylated dibenzanthronyls, dibenzanthrones, and isoclibenzanthrones in the same manner as in the case of the isothiouronium salts of the said chlormethylated compounds and Will dye directly from aqueous solutions. Although the quaternary salts are less fast to light than the isothiouronium salts, the former nevertheless are fast to chlorine and Washing. Both the isothiouronium and quaternary salts have also shown utility as bactericides, fungicides, and insecticides.

Of the isothiouronium salts of the chlormethylated dibenzanthronyl, dibenzanthrone, and isodibenzanthrone compounds, those which are derived from trimethyland tetramethylthiourea are preferred, and to insure suflicient solubility the halogenmethylated dibenzanthronyl, dibenzanthrone, or isodibenzanthrone compound should contain an average of at least one halogenmethyl group per molecule. Bright shades having ex- 2,619,492 I 3 4 cellent fastness to chlorine, washing, and light chloromethyldibenzanthronyl, 18.7 gr. of 1,3-diare obta ned w n printing these isothiouronium methylthiourea, and 35 ml. of water was heated salts of the chlormethylated dibenzanthronyl, di under eflux (1014020 C for 30 minutes The benzanthrone, and isodibenzanthrone comresulting Solution was cooled to 0 and pounds 5 then poured into 200 ml. of acetone. The precip- As starting materials for the production of t n t d filt h d 7 th 1 a ed solid was co co e on a or, was e W1 the lsothlouromum and quatemary Salts e acetone, and dried. 3.7 gr. of a yellow product class of chlormethylated dibenzanthronyl, dibenzanthrone, and isodibenzanthrone compounds were Obtalned- T1115 Product punts cotton. 1n described in application Serial No. 143,596, filed 10 bright yellow shades from an aqueous SO ut O on February 10, 1950, may be employed. This The product has the formula:

CHzHN NHCH:

class includes dibenzanthronyl, dibenzanthrone, EXAMPLE 3 isodibenzanthrone and such compounds containl mg nuclear substituents such as halogen 0 The 1,1,3,3-tetramethylzsotlnouromum salt of dzstituents, and in addition at least one halomethyl chloromethyl-33"dlbenzanthmnyl group per molecule. Monoand dichlormethyl derivatives of the dibenzanthronyl, dibenzanthrone, and isodibenzanthrone compounds are A mixture of 2.8 gr. of dichloromethyl-3,3- dibenzanthronyl and 12 gr. of 1,1,3,3-tetramethylmost commonly obtained by the process of thiourea was heated at 110 C. for 10 minutes. plication Serial No. 143,596, filed on February 10, The e ow i o ur m a s s d by 1950. However, the product of the chlormethylapouring the reaction mixture into acetone, filtertion process may contain an average of one chloring, washing with acetone, and drying. 4.3 gr.

m y group 0 a a t of from 1 t0 3 Chlorof a yellow solid product, which dyes cotton bright methyl groups and Such products may be readily yellow shades from aqueous soluton, were obconverted to the isothiouronium and quaternary mined Salts by the process of this applicatmn' A mixture of 60% of this dye and 40% of Alcian The following examples will serve to further illustrate the invention, but it is not intended that 35 Blue punts bnght green shades Wlth they should be considered as limitations on the improve? fastnesslo light and Washing as scope of the invention. Unless otherwise stated, pared Wlth e Alclan Blue- The p uc s e the parts are by weight. formula:

(CH1)ZN\ /N(CH:): of os-oN2@ CHSC o1 (CHzhN morn),

EXAMPLE 1 EXAMPLE 4 The 1,1,3-trimethylisothiouronium salt of dichloromethyldibenzanmmne (violanthmne) The trimethylammonium salt of dichloromethyl- 4,4'-dibenzanthronyl (C. A. 4,4'-Bi-7H-benz- A mechanically stirred mixture of 6 er. of did th 7- H D chloromethyldibenzanthrone, 6 gr. of 1,1,3-trimethylthiourea, and 35 ml. of water was heated Into an autoclave equipped with an agitator, a

under reflux (101-102 C.) for 30 minutes. The thermometer, and a pressure gauge was placed resulting solution was cooled to 40-50 C. and 23.5 grams of dichloromethyl-4,4-dibenzanthrothen poured into 200 ml. of acetone. The precipnyl and 46.0 grams of trimethylamine dissolved itated solid was collected on a filter, washed with in 410 grams of absolute ethanol. The reaction acetone, and dried. 6 gr. of a brown product mixture was heated at 115-120 C. (pressure were obtained. An aqueous solution of this maequals 80 p. s. i.) for 3 hours. On cooling, the terial dyes cotton in violet shades of good fastmixture was filtered to remove any insoluble maness to light. The product has the formula: terial (discarded). The yellow filtrate was con- 0 o (CHZ)2N\ v N(CH1): o1 cs-on=-O CH:SO\ o1 omHN NHCH:

EXAMPLE 2 centrated on a steam bath under reduced pressure and upon dilution with acetone the product The 1,3-dzmethylzsothzouromum salt of dzchlorowas precipitated in 80% yi 81d. This dye prints methyz'3sdibenzanthmnyz cotton in yellow shades. The product has the A mechanically stirred mixture of 5.5 gr. of di formula:

2,619,492 6 EXAMPLE 5 I claim:

The 1,1Q3-trimethylisothiouronium salt of chloro- 'f soluble onium salts of halogenmethyl methyzisobenzanmmne derivatives of vat dyes of the class consisting of those havin the formulae: A reaction mixture consisting of 30 g. of chloro- 5 g methylisodibenzanthrone, 30 gr. of 1,1,3-trimeth- (1) h R ylthiourea, and 120ml. of water was heated under y reflux (101-102 C.) for 30 minutes. The result- CHQSO ing solution was cooled to 40-50 C. and then 7 Nam;- poured into 200 ml. of acetone. The precipi- 10 tated solid was collected on a filter, washed with N Q QN acetone, and dried. The yield was 23 gr. of a (3) +f-r product which prints cotton in dull violet shades of excellent light fastness from an aqueous solution. The product has the formula: wherein Ar is a dibenzanthronyl radical selected 0 /];I(CH:)1 Oom-so of NHCH:

0 EXAMPLE 6 from the group consisting of the following structural configurations:

The 1,1,3-trimethylisothiouronium salt of di- 25 0 O chloromethylisodibenzanthrone A reaction mixture of gr. of dichloromethyl- O isodibenzanthrone, gr. of 1,1,3-trimethylthiourea, and 42 ml. of water was heated under an reflux (HO-102 C.) for minutes. The resultd O 0 ing solution was cooled to -50 C. and then poured into 200 ml. of acetone. The precipitated solid was collected in a filter, washed with acetone, O

and dried. 16.2 gr. of the product were obtained.

The product has the formula: 35 R1, R2, R3, and R4 are members of the group con- /1(CH3)2 K Gone-so: oi (CHs)z NHCH; c1 /OSCH CHaHN EXAMPLE '7 sisting of alkyl, alkylene, aryl, and hydrogen,

of which R2 and R4 may together form a closed The pyrzdmzum salztazghigzheloromethylisodzben ring system; Q1, Q2, and Q3 are members of the group consisting of alkyl, alkylol, and alkaryl; Z 11.5 gr. of dichloromethylisodibenzanthrone indicates the C atoms necessary to complete a and 200 ml. of pyridine are heated in an auto- 6-membered ring system; A indicates a negative clave at 150 C. for 1 hours. The reaction mixion; and n is a number from 1 to 3. ture is filtered and washed with acetone. The 2. The isothiouronium salt of dichloromethylyield is 12.7 gr. of the resulting pyridinium salt. 3,3-dibenzanthronyl having the formula:

o o CHaHN NHCH: u a Cl osoHZ- O-om-so o1 GHaHN NHCH; This dye prints cotton in bright violet shades and 3. The isothiouronium salt of dichloromethylhas bactericidal, fungicidal, and insecticidal prop- 3,3-dibenzanthronyl having the formula:

(CH3):N N(CHa)z 0T /CS-CH2 om-so 0T (CHa)2N N(OHz) erties. The product has the formula:

0 0H-o CH C. a G i 3 \i 011:0]: HC\ N-OHr-6 \0 01 DAVID I. RANDALL. (References on following page) 7 REFERENCES CITED The following references are of record inthe file of this patent:

UNITED STATES PATENTS Number Name Date 2,189,397 Harris Feb. 6, 1940 2,189,720 Watt Feb. 6, 1940 2,302,885 Orthner Nov. 24, 1942 2,544,825 Coffey et a1 Mar. 13, 1951 10 8 FOREIGN PATENTS Number Country Date 613,980 Great Britain Dec. 7, 1948 623,998 Great Britain May 26, 1949 OTHER REFERENCES Taylor et a1., Sidgwicks Organic Chemistry of Nitrogen, page 27, 1945, Oxford at the Clarendon Press. 

1. THE SOLUBLE ONIUM SALTS OF HALOGENMETHYL DERIVATIVES OF VAT DYES OF THE CLASS CONSISTING OF THOSE HAVING THE FORMULAE: 